Thenyl phosphorothioates



United States Patent 3,205,238 THENYL PHOSPHOROTHIOATES Kenneth L.Godfrey, Kirkwood, Mo., assignor to Monsanto Company, St. Louis, Mo., acorporation of Delaware No Drawing. Continuation of application Ser. No.20,561, Apr. 7, 1960. This application Oct. 16, 1964,

Ser. No. 404,522

8 Claims. (Cl. 260--332.5)

The present application is a continuation of copending application,Serial Number 20,561, filed April 7, 1960, now abandoned.

This invention relates to new and usefulphosphorothioates, to methods ofmaking same, and to insecticidal compositions containing same as anactive ingredient.

The new phosphorothioates can be termed thienyl phosphorothioates andemploying the skeleton of the thiophene radical can be represented bythe structure yumm al y e RQ X l X A RIIO wherein R and R are like orunlike lower alkyl radicals (i.e. alkyl radicals containing from 1 tocarbon atoms such as methyl, ethyl, propyl, butyl, amyl, and the variousisomeric forms thereof) .but preferably alkyl radicals containing notmore than two carbon atoms, wherein X and X are chalkogens of atomicweight less than 40 (i.e. sulfur or oxygen) but wherein at least one ofX and X is sulfur, and wherein A is an aliphatic hydrocarbon radicalhaving the empirical formula C H wherein n is a whole number from 1 to 3but preferably 1; and wherein the sum total of a, b and e (i.e. a+b+e)is an integer from 0 to 3, inclusive, but preferably an integer from 0to 2, inclusive.

The preferred thienyl phosphorothioates of this inven-v tion are thethenyl phosphorothioates of the structure wherein R and Rf are alkylradicals containing not more than two carbon atoms; wherein X and X arechalkogens of atomicweight less than.40 but wherein at least one of Xand X is sulfur; wherein Hal means a halogen having an atomic numberabove 9 butnot higher than 35 (i.e. chlorine or bromine); wherein alky1-means an alkyl radical containing not more than two carbon atoms;wherein b is an integer from 0 to 2, inclusive; wherein e is an integerfrom 0 to 2, inclusive; and wherein the sum total of b and e is aninteger from 0 to 2, inclusive.

Thienyl phosphorothioates of the foregoing structures wherein X issulfur can be prepared by reacting a salt (i.e. ammonium or alkali metalsuch as sodium, potas sium or lithium) of a phosphorothioic acid of thestructure P-SH wherein R, R" and X have the aforedescribed significance,with a substantially equimolecular proportion of a halide of thestructure (Hal) b halogen. A

wherein A, a, b, Hal, e and alkyl have theaforedescribed significanceand wherein the term halogen means a halogen having an atomic numberabove 9 but not higher than 35 (i.e. chlorine or bromine) in thepresence of an inert organic liquid or solvent (e.g acetone, butanone,dioxane, benzene, toluene, Xylene, ethyl alcohol, isopropyl alcohol,etc.). Whilea wide range of reactiontemperatures can be employedprovided the reaction systemis fluid (i.e. a temperature above thefreezing point of the systemand up to and including the boiling point ofthe system), it is preferred to employ a reaction temperature in therange of 20 C. to C.

Thienyl phosphorothioates of theforegoing structure wherein X is sulfurand wherein X is oxygencan be pre pared by reacting aphosphorohalidithioate of the structure wherein halogen means a halogenhaving an atomic number, above 9 but not higher than 35 (i.e. chlorineorbromine), with anequimolecular proportion of athienyl substitutedalcohol of the structure HO i ing agent (e.g. sodium carbonate,potassium carbonate, the tertiary organic amines such as triethylamine,tribu tylamine, dimethylaniline, lutidine, pyridine, etc.) in an amountsuflicient to absorb the hydrogen halide byproduct. While a wide rangeof reaction temperatures can be employed provided the system is fluid(i.e. a temperature above the freezing point of the system and up to andincluding the boiling point of the system) it is preferred to employ atemperature in the range of 20 C. to 120 C.

As illustrative of the new phosphorothioates of this invention is thefollowing S- (Z-thenyl) 0,0-dimethyl phosphorothioate O-(Z-thenyl)0,0-dimethyl phosphorothioate S-(Z-thenyl) 0,0-dimethylphosphorodithioate S-(3-thenyl) 0,0-dimethyl phosphorothioateS-(3-thenyl) 0,0-diisopropyl phosphorodithioate S-(Z-thenyl)0,0-di-n-buty1 phosphorothioate S-(Z-thenyl) 0,0-diisoamy-lphosphorodithioate O-(3-thenyl) 0,0,diethyl phosphorothioateO-(S-chloro-Z-thenyl) 0,0-diethy1 phosphorothioate S-(S-chloro-Z-thenyl)0,0-dimethyl phosphorothioate S(-chloro-2-thenyl) 0,0-diethylphosphorodithioate S-(S-bromo-Z-thenyl) 0,0-diethyl phosphorothioateS-(2-nitro-3-thenyl) 0,0-diethyl phosphorodithioate S-(3-nitro-2-thenyl)0,0-dimethyl phosphorodithioate S-(2,5-dichloro-3-thenyl) 0,0-diethylphosphorothioate O-(S-n-butyl-Z-thenyl) 0,0-diethyl phosphorothioateO-(S-ethyI-Z-thenyl) 0,0-diisopropyl phosphorothioateS-(3-methyl-2-thenyl) 0,0-dimethyl phosphorodithioateS-(2,5-diethy1-3-thenyl) 0,0-diethyl phosphorodithioateS-(2-methyl-3-thenyl) 0,0-diethyl phosphorothioateS-(5-chloro-4-methyl-2-thenyl) 0,0-dimethyl phosphorodithioateS-(2-bromo-3-thenyl) 0,0-dimethyl phosphorodithioateS-(2,5-dimethyl-3-thenyl) 0,0-diethyl phosphorothioateS-(2,5-dibromo-3-thenyl) 0,0-diethyl phosphorothioateS-(S-isopropyl-Z-thenyl) 0,0-diethyl phosphorothioateS-(4-chl0ro-3-thenyl) 0,0-diethyl phosphorodithioateS-(2,5-diethyl-3-chloro-4-thenyl) 0,0-diethyl phosphorothioateS-(Z-methyl-3-chloro-S-tert.butyl-4-thenyl) 0,0-diethyl phosphorothioateS-(2,5-dimethyl-3-chloro-4-thenyl) 0,0-diethyl phosphorodithioateS-[1-(2-thienyl)ethyl] 0,0-diethyl phosphorodithioate S-[Z-(2-thienyl)ethyl] 0,0-diethyl phosphorothioate S-[2-(2-thienyl)propyl]0,0diethyl phosphorothioate S-[l-(S-chloro-Z-thienyl) ethyl]0,0-dimethyl phosphorodithioate As illustrative of the preparation ofthe phosphorothioates of this invention is the following:

Example I To a suitable reaction vessel equipped with a thermometer,agitator and reflux condenser is charged 55.8 parts by weight(substantially 0.3 mole) of 0,0-diethyl phosphorodithioic acid and 99.0parts by weight of a 20.8% solution of sodium ethylate (substantially0.3 mole) in ethyl alcohol. To this ethyl alcohol solution of sodium0,0-diethyl phosphorodithioate is added 39.8 parts by weight(substantially 0.3 mole) of Z-thenyl chloride. The reaction mass is thenheated for 2.5 hours at about 80 C. The resulting reaction mass is thencooled to room temperature and quenched with water. The organic layer isremoved and washed first with 3% aqueous sodium carbonate and thenwithwater. The so-washed organic solution is then heated at 100 C. at 25mm. pressure to remove the volatiles. The residue, 78.1 parts by Weightof an amber liquid, is S-(Z-thenyl) 0,0-diethyl phosphorodithioate,which is soluble in benzene, ethyl ether and chloroform but insoluble inwater. Analysis.Theory: 34.0% S. Found: 33.8% S.

Example II To a suitable reaction vessel equipped with a thermometer,agitator and reflux condenser is charged 71.0 parts by weight(substantially 0.35 mole) of ammonium 0,0- diethyl phosphorodithioate,approximately 160 parts by weight of acetone, and 50.1 parts by weight(substantially 0.30 mole) of 5-chl-oro-2-thenyl chloride. The mass isthen heated slowly to the reflux temperature and then refluxed for 1.25hours. The resulting reaction mass is then cooled to room temperatureand quenched with water. The organic layer is removed and washed firstwith 3% aqueous sodium carbonate and then with water. The so-washedorganic solution is then dissolved in ben zene and then dried bydistilling oil the volatiles by heating to final conditions of 105 C. at20 mm. pressure. The residue, 91.0 parts by weight of an amber liquid,is S-(S-chloro 2 thenyl) 0,0-diethyl phosphorodithioate which is solublein chloroform, ethyl alcohol and ethyl acetate but insoluble in water.Analysis.Theory: 9.8% P, 11.2% C1. Found: 10.0% P, 10.9% Cl.

Example 111 Employing the procedure of Example 11 but replacing ammonium0,0-diethyl phosphorodithioate with an equimolar amount of ammonium0,0-diethyl phosphorothioate there is obtained in a 98.2% yieldS-(S-chloro-Z- thenyl) 0,0-diethyl phosphorothioate, an oil, which issoluble in ethyl alcohol, ethyl acetate, and chloroform but insoluble inwater. Analysis.Theory: 11.8% Cl, 10.3% P. Found: 11.7% Cl, 10.8% P.

Example IV Employing the procedure of Example II but replacing ammonium0,0-diethyl phosphorodithioate with an equimolecular amount of ammonium0,0-dimethyl phos phorodithioate there is obtained in an "88.6% yieldS-(S- chloro-2-thenyl) 0,0-dimethyl phosphorodithioate, an oil, which issoluble in ethyl alcohol and carbon tetrachloride but insoluble inwater.

Example V Employing the procedure of Example 11 but replacing ammonium0,0-diethyl phosphorodithioate with an equimolecular amount of ammonium0,0-diis0propyl phosphorodithioate there is obtained in a yield S-(S-chloro-2-thenyl) 0,0-diisopropyl phosphorodithioate an amber liquidwhich is soluble in diethyl ether, and chloroform but insoluble inwater. Analysis.Theory: 9.0% P. Found: 9.3% P.

Example VI Employing the procedure of Example 11 but replacing5-chloro-2-thenyl chloride with an equimolar amount of Z-thenyl bromideand replacing ammonium 0,0-diethyl phosphorodithioate with an equimolaramount of sodium 0,0-diethyl phosphorothioate there is obtained S-(2-thenyl) 0,0-diethyl phosphorothioate, an oil which is soluble inchloroform and ethyl acetate but insoluble in water.

Example VII Employing the procedure of Example II 'but replacing5-chloro-2-thenyl chloride with an equimolar amount of2,5-dichloro-3-thenyl chloride there is obtained S- (2,5-dichlor-oS-thenyl) 0,0-diethyl phosphorodithioate, an oil which is soluble inchloroform but insoluble in water.

Example VIII Employing the procedure of Example I but replacing Z-thenylchloride with an equimolar amount of 2- (2bromoethyl) thiophene there isobtained S-[2-(2-thienyl)- ethyl] 0,0-diethyl phosphorodithioate, an oilwhich is soluble in chloroform but insoluble in water.

Example IX To a suitable reaction vessel equipped with a thermometer,agitator and reflux condenser is charged approximately 200 parts byweight of benzene, 18.8 parts by weight (substantially 0.1 mole) of0,0-ethyl phosphorochl-oridothi-oate, 11.4 parts by weight(substantially 0.1 mole) of Z-thienylmethanol, and 7.9 parts by weight(substantially :1 mole) of pyridine. The mixture is refluxed for 8hours, cooled to room temperature and filtered. The filtrate is thenwashed first with 3% aqueous sodium ca bonate and then with water. Theso-washed organic solution is'then subjected to vacuum distillation toremove the benzene. The residue, a liquid, is O-(Z-thenyl) 0,0-diethylphosphorothioate which is soluble in acetone, ethyl alcohol, and ethylacetate but insoluble in water.

Example X Employing the procedure of Example 11 but replacingS-chloro-Z-thenyl chloride with an equimolar amount of 2-nitro-3-thenylbromide there is obtained S-r(2-nitro-3- thenyl) 0,0-diethylphosphorodithioate which is soluble in acetone but insoluble in water.

Example XI Employing the procedure of Example 11 but replacingS-chloroaZ-thenyl chloride with an equimolar amount of5-chloro-4methyl-2-thenyl chloride there is obtained S-(S-chlor0-4-methyl-2-thenyl) 0,0-diethyl phosphorodithioate, an oil whichis insoluble in water.

Example XII Employing the procedure of Example IX but replacingZ-thienyl methanol with an equirnolar amount of 2-(2- thienyl)ethanolthere is obtained O-[2-(2-thienyl)ethyl] 0,0-diethyl phosphorothioate,an oil which is water insoluble.

Example XIII Employing the procedure of Example I but replacing 2-thenylchloride with an equimolar amount of 1-(2- thienyD-I-chloroethane thereis obtained S-[1-(2-thienyl)- ethyl] 0,0-diethyl phosphorodithioate, anoil, which is soluble in benzene but insoluble in water.

The methods by which the phosphorothioates of this invention areisolated will vary slightly with the reactants employed and the productproduced. Further purification by selective solvent extraction or byabsorptive agents such as activated carbon or clays can precede theremoval of the inert organic liquid or solvent. Additionally an inertorganic solvent can be added to and in the purification by absorptiveagents. However, the product is generally satisfactory for insecticidalpurposes without furthe purification.

It will be understood that the terms insect and insecticide are usedherein in their broad common usage to in clude spiders, mites, ticks,and like pests which are not in the strict biological sense classed asinsects. Thus, the usage herein conforms to the definitions provided byCongress in Public Law 104, the Federal Insecticide, Fungicide, andRodenticide Act of 1947, Section 2, subsection h, wherein the terminsect is used to refer not only to those small invertebrate animalsbelonging mostly to the class Insecta, comprising six-legged, usuallywinged forms, as beetles, bugs, bees, flies, and so forth, but also toother 6. allied classes of arthropods whose members are Wingless andusually have more than six legs, as spiders, mites, ticks, centipedes,and wood lice.

The phosphorothioates of this invention are effective against a widevariety of insect pests. As illustrative of the activity but notlimit-ative thereof is the following:

One gram of S-(2-thenyl) 0,0-diethyl phosphorodithioate is dissolved insufficient acetone to make a concentrate solution thereof. Approximately0J1 cc. of sorbitan monolaurate polyoxyethylene derivative (a commercialwatersoluble non-ionic emulsifying agent) is then mixed with theconcentrate. To this mixture and with agitation is added sufficientwater to provide an aqueous emulsion having a concentration of 0.05% byweight of S (2-thenyl) 0,0-diethyl phosphorodithioate. Thereupon limabean plant leaves previously infested with the two spotted spider mite,T etraanychus telarius (L), are dipped in the aqueous emulsion,withdrawn, and set aside for observation. At the end of 48 hours a 100%kill of the mobile stage of the mite was noted. Seven days after settingthe test specimen aside residual activity was confirmed, a 100% kill ofthe resting stage and a 97% kill of the ova stage being noted. Similarresults against the mobile resting and ova stages of the same mite wereobtained employing S-(S-chloroQ-thenyl) 0,0-diethyl phosphorodit'hioateinstead of S'(2-thenyl) 0,0-diethy1 phosphorodithioate at aconcentration of 0.1%. Similar results were obtained employingS-(S-chloro-Z-thenyl) 0,0-diethyl phosphorothioate.

Contact activity was also observed employing the compounds of thisinvention against larvae of the Mexican bean beetle, e.g. at aconcentration of 0.05% by weight. 8- (Z-thenyl) 0,0-diethylphosphorodithioate gave a kill.

Employing S-(Z-thenyl) 0,0-diethyl phosphorodithioate andS-(5-chloro-2-thenyl) 0,0-diethyl phosphorodithioate, respectively, at aconcentration of 0.0005% by weight against yellow fever mosquito larvae,Aedes aegypti, 100% kill in each instance was observed.

Systemic activity was also observed against a wide variety of insects.For example against the two-spotted spider mite, Tetranychus telarius(L.), a 100% kill was observed employing S-(S-chloro-Z-thenyl)0,0-diethyl phosphorothioate at a concentration of 0.004% by weight.

Although the phosphorothioates of this invention are useful per se incontrolling a wide variety of insect pests, it is preferable that theybe supplied to the pests or to the environment of the pest or pests in adispersed form. in a suitable extending agent.

In the instant specification and appended claims it is to be understoodthat the term dispersed is used in its widest possible sense. When it issaid that the phosphorothioates of this invention are dispersed, itmeans that the particles of the phosphorothioates of this invention maybe molecular in size and held in true solution in a suitable organicsolvent. It means further, that the particles may be colloidal in sizeand distributed throughout a liquid phase in the form of suspensions oremulsions or in the form of particles held in suspension by wettingagents. It also includes particles which are distributed in a semi-solidviscous carrier such as petrolatum or soap or other ointment base inwhich they may be actually dissolved in the semi-solid or held insuspension in the semi-solid with the aid of suitable wetting oremulsifying agents. The term dispersed also means that the particles maybe mixed with and distributed throughout a solid carrier providing amixture in particulate form, e.g. pellets, granules, powders, or dusts.The term dispersed also includes mixtures which are suitable for use asaerosols including solutions, suspensions, or emulsions of thephosphorothioates of this invention in a carrier such asdichlorodifluoromethane and like fluorochloroalkanes which boil belowroom temperature at atmospheric pressure.

In the instant specification and appended claims it is to be understoodthat the expression extending agent includes any and all of thosesubstances in which the phosphorothioates of this invention aredispersed. It includes, therefore, the solvents of a true solution, theliquid phase of suspensions, emulsions or aerosols, the semi-solidcarrier of ointments and the solid phase of particulate solids, e.g.pellets, granules, dusts and powders.

The exact concentration of the phosphorothioates of this inventionemployed in combatting or controlling insect pests can vary considerablyprovided the required dosage (i.e., toxic or lethal amount) thereof issupplied to the pests or to the enviroment of the pests. When theextending agent is a liquid or mixture of liquids (eg. as in solutions,suspensions, emulsions, or aerosols) the concentration of thephosphorothioate employed to supply the desired dosage generally will bein the range of 0.001 to 50 percent by weight. When the extending agentis a semi-solid or solid, the concentration of the phosphorothioateemployed to supply the desired dosage generally will be in the range of0.1 to 25 percent by weight. From a practical point of view, themanufacturer must supply the agriculturist with a low-cost concentrateor spray base or particulate solid base in such form that, by merelymixing with water or solid extender (e.g., powdered clay or talc) orother low-cost material available to the agriculturist at the point ofuse, he will have an easily prepared insecticidal spray or particulatesolid. In such a concentrate composition, the phos phorothioategenerally will be present in a concentration of to 95 percent by weight,the residue being any one or more of the well-known insecticidaladjuvants, such as the various surface active agents (e.g., detergents,a soap or other emulsifying or wetting agent, surface-active clays),solvents, diluents, carrier media, adhesives, spreading agents,humectants, and the like.

There are a large number of organic liquids which can be used for thepreparation of solutions, suspensions, or emulsions of thephosphorothioates of this invention. For example, isopropyl ether,acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbontetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptaneand like higher liquid alkanes, hydrogenated naphthalenes, solventnaphtha, benzene, toluene, xylene, petroleum fractions (e.g. thoseboiling almost entirely under 400 F, at atmospheric pressure and havinga flash point above about 80 F., particularly kerosene), mineral oilshaving an unsulfonatable residue above about 80 percent and preferablyabove about 90 percent. In those instances Wherein there may be concernabout the phytoxicity of the organic liquid extending agent a portion ofsame can be replaced by such low molecular weight aliphatic hydrocarbonsas dipentene, diisobutylene, propylene trimer, and the like or suitablepolar organic liquids such as the aliphatic ethers and the aliphaticketones containing not more than about carbon atoms as exemplified byacetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropylether, and the like. In certain instances, it is advantageous to employa mixture of organic liquids as the extending agent.

When the phosphorothioates of this invention are to be supplied to theinsect pests or to the environment of the pests as aerosols, it isconvenient to dissolve them in a suitable solvent and disperse theresulting solution in dichlorodifiuoromethane or like chlorofluoroalkanewhich boils below room temperature at atmospheric pressure. 7 Thephosphorothioates of this invention are preferably supplied to theinsect pests or to the environment of the insect pests in the form ofemulsions or suspensions. Emulsions or suspensions are prepared bydispersing the phosphorothioate of this invention either per se or inthe form of an organic solution thereof in water with the aid of awater-soluble surfactant. The term surfactant as employed here and inthe appended claims is used as in volume II of Schwartz, Perry andBerchs Surface Active Agents and Detergents (1958, IntersciencePublishers, Inc, New York), in place of the expression emulsifying agentto connote generically the various emulsifying agents, dispersingagents, wetting agents and spreading agents that are adapted to beadmixed with the active compounds of this invention in order to securebetter wetting and spreading of the active ingredients in the watervehicle or carrier in which they are insoluble through lowering thesurface tension of the water (see also Frear, Chemistry of Insecticides,Fungicides and Herbicides, second edition, page 280). These surfactantsinclude the well-known capillary-active substances which may beanion-active (or anionic), cation active (or cationic), or non-ionizing(or non-ionic) which are described in detail in volumes I and II ofSchwartz, Perry and Berchs Surface Active Agents and Detergents (1958,Interscience Publishers, Inc., New York), and also in the November 1947issue of Chemical Industries (pages 811-824) in an article entitledSynthetic Detergents by John W. McCutcheon and also in the July, August,September and October 1952 issues of Soap and Sanitary Chemicals underthe title Synthetic Detergents. The disclosures of these articles withrespect to surfactants, i.e. the anion active, cation-active andnonionizing capillary active substances, are incorporated in thisspecification by reference in order to avoid unnecessary enlargement ofthis specification. The preferred surfactants are the water-solubleanionic surface-active agents and the water soluble non-ionicsurface-active agents set forth in US. 2,846,398 (issued August 5,1958). In general it is preferred that a mixture of water-solubleanionic and water-soluble non-ionic surfactants be employed.

The phosphorothioates of this invention can be dispersed by suitablemethods (e.g., tumbling or grinding) in solid extending agents either oforganic or inorganic nature and supplied to the insect pest environmentin particulate form. Such solid materials include for example,tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc,bentonite, fullers earth, pyrophillite diatomaceous earth, calcinedmagnesia, volcanic ash, sulfur and the like inorganic solid materials,and include, for example, such materials of organic nature as powderedcork, powdered wood, and powdered walnut shells. The preferred solidcarriers are the adsorbent clays, e.g. bentonite. These mixtures can beused for insecticidal purposes in the dry form, or, by addition ofwatersoluble surfactants or wetting agents the dry particulate solidscan be rendered wettable by water so as to obtain stable aqueousdispersions or suspensions suitable for use as sprays.

For special purposes the phosphorothioates of this invention can bedispersed in a semi-solid extending agent such as petrolatum or soap(e.g., sodium stearate or oleate or palmitate or mixtures thereof) withor without the aid of solubility promoters and/or surfactants ordispersing agents.

In all of the forms described above the dispersions can be providedready for use in combatting insect pests or they can be provided in aconcentrated form suitable for mixing with or dispersing in otherextending agents. As illustrative of a particularly useful concentrateis an intimate mixture of phosphorothioates of this invention with awater-soluble surfactant which lowers the surface tension of water inthe weight proportions of 0.1 to 15 parts of surfactant with sufiicientof the phosphorothioate of this invention to make 100 parts by weight.Such a concentrate is particularly adapted to be made into a spray forcombatting various forms of insect pests (particularly mites) by theaddition of water thereto. As illustrative of such a concentrate is anintimate mixture of parts by weight of S-(5-chloro-2-thenyl) 0,0-diethylphosphorodithioate and 5 parts by weight of a water-soluble nonionicsurfactant such as the polyoxyethylene derivative of sorbitanmonolaurate.

Another useful concentrate adapted to be made into a spray forcombatting insect pests (particularly mites) is a solution (preferablyas concentrated as possible) of a phosphorothioate of this invention inan organic solvent therefor. The said liquid concentrate preferablycontains dissolved therein a minor amount (e.g. 0.5 to 10 percent byweight of the weight of the new insecticidal agent) of a surfactant (oremulsifying agent), which surfactant is also water-soluble. Asillustrative of such a concentrate is a solution ofS-(S-chloro-Z-thenyl) 0,0-diethyl phosphorothioate in benzene whichsolution contains dissolved therein a water-soluble polyoxyethyleneglycol nonionic surfactant and a water-soluble alkarylsulfonate anionicsurfactant.

Of the surfactants aforementioned in preparing the various emulsifiable,wettable or dispersible compositions or concentrates of this invention,the anionic and nonionic surfactants are preferred. Of the anionicsurfactants, the particularly preferred are the well-known watersolublealkali metal alkylarylsulfonates as exemplified by sodium decylbenzenesulfonate and sodium dodecylbenzene sulfonate. Of the nonionicsurfactants, the particularly preferred are the water-solublepolyoxyethylene derivations of alkylphenols (particularlyisooctylphenol) and the water-soluble polyoxyethylene derivatives of themono-higher fatty acid esters of hexitol anhydrides such as mannitan orsorbitan.

In all of the various dispersions described hereinbefore forinsecticidal purposes, the active ingredients can be one or more of thecompounds of this invention. The compounds of this invention can also beadvantageously employed in combination with other pesticides, including,for example, nematocides, bacterocides, and herbicides. In this mannerit is possible to obtain mixtures which are effective against a widevariety of pests and other forms of noxious life.

In controlling or combatting insect pests the phosphorothioates of thisinvention either per se or compositions comprising same are supplied tothe insect pests or to their environment in a lethal or toxic amount.This can be done by dispersing the new insecticidal agent orinsecticidal composition comprising same in, on or over an infestedenvironment or in, on or over an environment the insect pests frequent,e.g. agricultural soil or other growth media or other media infestedwith the insect pests or attractable to the pests for habitational orsustenance or propagational purposes, in any conventional fashion whichpermits contact between the insect pests and the phosphorothioates ofthis invention. Such dispersing can be brought about by applying thephosphorothioates per se or sprays or particulate solid compositionscontaining same to a surface infested with the insect pests orattractable to the pests, as for example, the surface of agriculturalsoil or other media such as the above ground surface of plants by 'anyof the conventional methods, e.g. power dusters, boom and hand sprayers,and spray dusters. Also for sub-surface application such dispersing canbe carried out by simply mixing the new insecticidal agent per se orinsecticidal spray or particulate solid compositions comprising samewith the infested environment or with the environment the insect pestsfrequent, or by employing a liquid carrier for the new insecticidalagent to accomplish subsurface penetration and impregnation therein.

While this invention has been described with respect to certainembodiments, it is to be understood that it is not so limited and thatvariations and modifications thereof obvious to those skilled in the artcan be made without departing from the spirit and scope thereof.

10 What is claimed is: 1. Thienyl phosphorothioates of the structure yie wherein a is an integer from 0 to 1, inclusive; wherein b is aninteger from 1 to 2, inclusive; wherein Hal means a halogen having anatomic number above 9 but not higher than 35; wherein e is an integerfrom 0 to 2, inclusive; wherein alkyl means alkyl having from 1 to 4carbon atoms; wherein R is f X -A- wherein R and R are lower alkyl,wherein X and X' are chalkogens of atomic weight less than 40 butwherein at least one of X and X is sulfur, and wherein A is of theempirical formula C H wherein n is a whole number from 1 to 3,inclusive, and wherein the sum total of a, b, and e is an integer from 1to 3, inclusive. 2. S-(5-chloro-2-thenyl) 0,0-diethylphosphorodithioate.

3. S-(5-chloro-2-thenyl) 0,0-dimethyl phosphorodithioate.

4. S-(5-chloro-2-thenyl) 0,0-diisopropyl phosphoro dithioate.

5. S-(5-chloro-2-thenyl) oate.

6. Thenyl 0,0-dialky1 phosphorothioates of the structure 0,0-diethylphosphorothi- P-XC H -(chloro substituted thienyl) structure P-S-CH Cl swherein R and R" are lower alkyl. 8. S-(2,5-dichloro-3-thenyl)0,0-diethyl phosphorodithioate.

of the References Cited by the Examiner UNITED STATES PATENTS 2,769,01310/56 Lowenstein-Lom 260-3323 2,862,017 11/58 Schrader et a1 2604612,957,007 10/60 McCall et al 260--332.5 2,964,528 12/60 Wicker et a1260294.8

WALTER A. MODANCE, Primary Examiner.

1. THIENYL PHOSPHOROTHIOATES OF THE STRUCTURE